Abstract
The primary mode of activation in chiral Lewis acid-catalyzed epoxide opening is polarization of the C-O σ-bond of the epoxide by coordination of a Lewis acid to the nonbonding electron pairs on the oxygen. Binding of the epoxide to the chiral Lewis acid activates the ring toward nucleophilic opening and places the enantiotopic carbons of the meso-epoxide within proximity to the influence of the chiral ligand on the Lewis acid. This chapter details the applications of chiral, nonracemic Lewis bases in the enantiodifferentiating reactions. In a detailed study on the mechanism of phosphoramide-catalyzed epoxide openings with SiCl4, Denmark and coworkers address questions regarding the stoichiometry, reaction kinetics, nonlinear effects, and the mode of activation for phosphoramide Lewis bases with SiCl4. The epoxide opening with SiCl4 produces an alkoxytrichlorosilane that can be susceptible to further Lewis base activation, leading to a dialkoxydichlorosilane and so forth.
| Original language | English (US) |
|---|---|
| Title of host publication | Lewis Base Catalysis in Organic Synthesis |
| Publisher | Wiley-VCH Verlag |
| Pages | 1113-1151 |
| Number of pages | 39 |
| Volume | 3 |
| ISBN (Electronic) | 9783527675142 |
| ISBN (Print) | 9783527336180 |
| DOIs | |
| State | Published - Aug 17 2016 |
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Keywords
- 1-aza[6]helicenes
- 1; 1'-biisoquinoline- N ; N -dioxide
- 29Si NMR
- 31 P NMR
- Allenylphosphine oxides
- BINAPO
- BITIPIO
- Bipyridyl- N -monooxide
- Bromohydrin
- Chlorohydrin
- Co(salen) complex
- Cooperative catalysis
- Desymmetrization
- Dual activation
- Electrophilic activation
- Epoxide
- Epoxide opening
- Fluorohydrin
- Halogenation
- Halohydrins
- Hexacoordinate
- Hydrohalogenation
- Kinetic resolution
- Meso-epoxides
- Nonlinear effects
- Nucleophilic activation
- Organotin halides
- Oxiranes
- PINDOX
- PINDY
- Pentacoordinate
- Phosphaferrocene
- Phosphametallocene
- Phosphine oxides
- Phosphoramides
- Pyridyl- N -oxides
- Silicon tetrachloride
- Siliconate
ASJC Scopus subject areas
- Chemistry(all)
Cite this
Reactions of epoxides (n → σ*). / Wilson, Tyler W.; Denmark, Scott E.
Lewis Base Catalysis in Organic Synthesis. Vol. 3 Wiley-VCH Verlag, 2016. p. 1113-1151.Research output: Chapter in Book/Report/Conference proceeding › Chapter
}
TY - CHAP
T1 - Reactions of epoxides (n → σ*)
AU - Wilson, Tyler W.
AU - Denmark, Scott E
PY - 2016/8/17
Y1 - 2016/8/17
N2 - The primary mode of activation in chiral Lewis acid-catalyzed epoxide opening is polarization of the C-O σ-bond of the epoxide by coordination of a Lewis acid to the nonbonding electron pairs on the oxygen. Binding of the epoxide to the chiral Lewis acid activates the ring toward nucleophilic opening and places the enantiotopic carbons of the meso-epoxide within proximity to the influence of the chiral ligand on the Lewis acid. This chapter details the applications of chiral, nonracemic Lewis bases in the enantiodifferentiating reactions. In a detailed study on the mechanism of phosphoramide-catalyzed epoxide openings with SiCl4, Denmark and coworkers address questions regarding the stoichiometry, reaction kinetics, nonlinear effects, and the mode of activation for phosphoramide Lewis bases with SiCl4. The epoxide opening with SiCl4 produces an alkoxytrichlorosilane that can be susceptible to further Lewis base activation, leading to a dialkoxydichlorosilane and so forth.
AB - The primary mode of activation in chiral Lewis acid-catalyzed epoxide opening is polarization of the C-O σ-bond of the epoxide by coordination of a Lewis acid to the nonbonding electron pairs on the oxygen. Binding of the epoxide to the chiral Lewis acid activates the ring toward nucleophilic opening and places the enantiotopic carbons of the meso-epoxide within proximity to the influence of the chiral ligand on the Lewis acid. This chapter details the applications of chiral, nonracemic Lewis bases in the enantiodifferentiating reactions. In a detailed study on the mechanism of phosphoramide-catalyzed epoxide openings with SiCl4, Denmark and coworkers address questions regarding the stoichiometry, reaction kinetics, nonlinear effects, and the mode of activation for phosphoramide Lewis bases with SiCl4. The epoxide opening with SiCl4 produces an alkoxytrichlorosilane that can be susceptible to further Lewis base activation, leading to a dialkoxydichlorosilane and so forth.
KW - 1-aza[6]helicenes
KW - 1; 1'-biisoquinoline- N ; N -dioxide
KW - 29Si NMR
KW - 31 P NMR
KW - Allenylphosphine oxides
KW - BINAPO
KW - BITIPIO
KW - Bipyridyl- N -monooxide
KW - Bromohydrin
KW - Chlorohydrin
KW - Co(salen) complex
KW - Cooperative catalysis
KW - Desymmetrization
KW - Dual activation
KW - Electrophilic activation
KW - Epoxide
KW - Epoxide opening
KW - Fluorohydrin
KW - Halogenation
KW - Halohydrins
KW - Hexacoordinate
KW - Hydrohalogenation
KW - Kinetic resolution
KW - Meso-epoxides
KW - Nonlinear effects
KW - Nucleophilic activation
KW - Organotin halides
KW - Oxiranes
KW - PINDOX
KW - PINDY
KW - Pentacoordinate
KW - Phosphaferrocene
KW - Phosphametallocene
KW - Phosphine oxides
KW - Phosphoramides
KW - Pyridyl- N -oxides
KW - Silicon tetrachloride
KW - Siliconate
UR - http://www.scopus.com/inward/record.url?scp=85018287225&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85018287225&partnerID=8YFLogxK
U2 - 10.1002/9783527675142.ch23
DO - 10.1002/9783527675142.ch23
M3 - Chapter
AN - SCOPUS:85018287225
SN - 9783527336180
VL - 3
SP - 1113
EP - 1151
BT - Lewis Base Catalysis in Organic Synthesis
PB - Wiley-VCH Verlag
ER -